CN106255728B - Hardenability silicon composition, its hardening thing and optical semiconductor device - Google Patents

Hardenability silicon composition, its hardening thing and optical semiconductor device Download PDF

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CN106255728B
CN106255728B CN201580006763.XA CN201580006763A CN106255728B CN 106255728 B CN106255728 B CN 106255728B CN 201580006763 A CN201580006763 A CN 201580006763A CN 106255728 B CN106255728 B CN 106255728B
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ingredient
sio
hardenability
silicon
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CN106255728A (en
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林昭人
西岛一裕
饭村智浩
须藤通孝
佐川贵志
小林昭彦
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Dow Toray Co Ltd
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Abstract

The present invention is a kind of hardenability silicon composition, and contain: (A) is with Unit formulas of Ping Jun: (R1 3SiO1/2)x(R2 2SiO2/2)y(R3SiO3/2)z(R1For alkyl, alkenyl, aryl or aralkyl, R2For alkyl or alkenyl, R3For alkyl, aryl or aralkyl, wherein R in a molecule1~R3At least 0.5 molar percentage be alkenyl, R3At least one be aryl or aralkyl, 0.01≤x≤0.5,0.01≤y≤0.4,0.1≤z≤0.9 and x+y+z=1) indicate organopolysiloxane；(B) organopolysiloxane of the straight-chain in a molecule at least two alkenyl；(C) organopolysiloxane of the hydrogen atom at least two and silicon atom bonding in a molecule；And (D) hydrosilylation reactions catalyst.The favorable dispersibility of the fluorophor of the hardenability silicon composition can be formed with cracking hardening thing.

Description

Hardenability silicon composition, its hardening thing and optical semiconductor device
Technical field
The present invention relates to a kind of hardenability silicon composition, the hardening thing of the composition and using made of the composition Optical semiconductor device.
Background technique
Sealing of the hardenability silicon composition for the optical semiconductor in optical semiconductor devices such as light emitting diode (LED) Agent, protective agent, smears etc..As such hardenability silicon composition, can illustrate: containing has at least two alkene in a molecule The organopolysiloxane of the straight-chain of base and at least one aryl, with averaged unit formula: (RSiO3/2)a(R2SiO2/2)b (R3SiO1/2)c(SiO4/2)d(XO1/2)eIn formula, R is identical or different monovalent hydrocarbon, wherein and in a molecule, the 0.1 of total R ~40 molar percentages are alkenyl, and 10 molar percentages of total R are the above are aryl, and X is hydrogen atom or alkyl, and a is positive number, b 0 Or positive number, c are 0 or positive number, d is 0 or positive number, and e is 0 or positive number, and the number that b/a is 0~10, c/a for 0~0.5 number, D/ (a+b+c+d) be 0~0.3 number, e/ (a+b+c+d) be 0~0.4 number indicate branched organopolysiloxane, one The organopolysiloxane and hydrosilylation reactions catalyst of hydrogen atom at least two and silicon atom bonding in molecule Hardenability silicon composition (referring to patent document 1 with 2)；Containing in a molecule at least two alkenyl and at least one aryl The organopolysiloxane of straight-chain, with averaged unit formula: (RSiO3/2)f(R2SiO2/2)g(R3SiO1/2)hIn formula, and R be it is identical or Different monovalent hydrocarbons, wherein in a molecule, 0.5 molar percentage of total R the above are alkenyl, 25 molar percentages of total R with Upper is aryl, and f, g and h are respectively to meet 0.30≤f≤0.60,0.30≤g≤0.55, f+g+h=1.00 and 0.10≤h/ (f + g)≤0.30 number indicate the organopolysiloxane of branched, there is in a molecule 2 aryl and at least of being at least averaged Average 2 with the organopolysiloxane of the hydrogen atom of silicon atom bonding and the hardenability of hydrosilylation reactions catalyst Silicon composition (referring to patent document 3).
In patent document 1 and 2, as the organopolysiloxane of branched, have without specifically recording with formula: R '2SiO2/2(in formula, R ' be identical or different carbon number be 1~12 alkyl or carbon number be 2~12 alkenyl) indicate silicon oxygen The organopolysiloxane of the branched of alkane unit.In addition, in patent document 3, recording following the description: relative to straight-chain 100 mass parts of organopolysiloxane, when the content of the organopolysiloxane of branched is more than 150 mass parts, the hardening thing of acquisition Adaptation decline for substrate, not preferably.
In general, such hardenability silicon composition mixture is for converting the fluorophor from the emission wavelength of LED and carrying out It uses, but the dispersibility of fluorophor is poor, therefore there are fluorophor to agglomerate, result generates not in the light from LED Uniform problem.Further, high current value is applied to the LED that the hardening thing using such hardenability silicon composition is sealed When making its continuous illumination, the problem of being cracked there is also hardening thing.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2004-143361 bulletin
Patent document 2: Japanese Patent Laid-Open 2005-105217 bulletin
Patent document 3: Japanese Patent Laid-Open 2008-001828 bulletin
Summary of the invention
Problems to be solved by the invention
It, can after the favorable dispersibility of fluorophor, hardening the purpose of the present invention is to provide a kind of hardenability silicon composition Being formed has cracking hardening thing.In addition, another object of the present invention is to provide a kind of hardening thing, the dispersion of fluorophor Property it is good, have it is cracking.Further, another object of the present invention is to provide a kind of optical semiconductor device, reliability is excellent It is different.
Technical solution
Hardenability silicon composition of the invention is characterized in that, is at least made of following substances:
(A) with averaged unit formula:
(R1 3SiO1/2)x(R2 2SiO2/2)y(R3SiO3/2)z
The organopolysiloxane of expression, in formula, R1For identical or different carbon number be 1~12 alkyl, carbon number be 2~12 Alkenyl, carbon number be 6~20 aryl or carbon number be 7~20 aralkyl, R2It is 1~12 for identical or different carbon number Alkyl or carbon number be 2~12 alkenyl, R3For carbon number be 1~12 alkyl, carbon number be 6~20 aryl or carbon number For 7~20 aralkyl, wherein in a molecule, with the R1、R2And R3At least 0.5 Mole percent of the summation of the group of expression Than for the alkenyl, with the R3At least one of the group of expression is the aryl or the aralkyl, x, y and z are respectively Meet the number of 0.01≤x≤0.5,0.01≤y≤0.4,0.1≤z≤0.9 and x+y+z=1.
(B) straight at least two alkenyl in a molecule of 0.1~60 mass parts relative to 100 mass parts (A) ingredient The organopolysiloxane of chain；
(C) hydrogen atom in a molecule at least two and silicon atom bonding organopolysiloxane relative to (A) at Divide with 1 mole of alkenyl total amount contained in (B) ingredient, rubs contained by this ingredient with the hydrogen atom of silicon atom bonding for 0.1~10 Your amount }；And
(D) hydrosilylation reactions catalyst, amount are to can promote the amount of this composition hardening.
Hardening thing of the invention is characterized in that, above-mentioned composition is hardened.
Optical semiconductor device of the invention is characterized in that, optical semiconductor is utilized to the hardening thing of above-mentioned composition Sealing covers.
Beneficial effect
It can be formed after favorable dispersibility of the hardenability silicon composition of the invention with fluorophor, hardening with cracking The feature of hardening thing.In addition, favorable dispersibility of the hardening thing of the invention with fluorophor, with cracking feature.Into one Step, optical semiconductor device of the invention have feature excellent in reliability.
Detailed description of the invention
Fig. 1 is the sectional view of the surface mounting LED of an example of optical semiconductor device of the invention.
Specific embodiment
Firstly, the hardenability silicon composition that the present invention will be described in detail.
(A) ingredient is with averaged unit formula:
(R1 3SiO1/2)x(R2 2SiO2/2)y(R3SiO3/2)z
The organopolysiloxane of expression.
In formula, R1For identical or different carbon number be 1~12 alkyl, carbon number be 2~12 alkenyl, carbon number be 6~20 Aryl or carbon number be 7~20 aralkyl.Methyl, ethyl, propyl, butyl, amyl, hexyl, heptan can specifically be illustrated The alkyl such as base, octyl, nonyl, decyl, undecyl, dodecyl；Vinyl, allyl, cyclobutenyl, pentenyl, hexenyl, The alkenyls such as heptenyl, octenyl, nonenyl, decene base, undecenyl, dodecenyl succinic；Phenyl, tolyl, xylyl, The aryl such as naphthalene, anthryl, phenanthryl, pyrenyl；The virtues such as benzyl, phenethyl, naphthylethyl, naphthalene propyl, anthracene ethyl, luxuriant and rich with fragrance ethyl, pyrene ethyl Alkyl；And with halogen atoms such as chlorine atom, bromine atoms partly or entirely instead of the base of the hydrogen atom with these group bondings Group.
In addition, in formula, R2For identical or different carbon number be 1~12 alkyl or carbon number be 2~12 alkenyl.Tool Body it can illustrate methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl Equal alkyl；Vinyl, allyl, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decene base, 11 carbon The alkenyls such as alkenyl, dodecenyl succinic；And with the halogen atoms such as chlorine atom, bromine atom partly or entirely instead of with these groups The group of the hydrogen atom of bonding.The R2It is preferred that all alkyl.
In addition, in formula, R3For carbon number be 1~12 alkyl, carbon number be 6~20 aryl or carbon number be 7~20 virtue Alkyl.Methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, hendecane can specifically be illustrated The alkyl such as base, dodecyl；The aryl such as phenyl, tolyl, xylyl, naphthalene, anthryl, phenanthryl, pyrenyl；Benzyl, phenethyl, The aralkyl such as naphthylethyl, naphthalene propyl, anthracene ethyl, luxuriant and rich with fragrance ethyl, pyrene ethyl；And with the halogen atoms such as chlorine atom, bromine atom part Or all instead of the group of the hydrogen atom with these group bondings.
In one molecule, with the R1、R2And R3The summation of the group of expression, i.e. with total organic group of silicon atom bonding At least 0.5 molar percentage is the alkenyl, preferably vinyl.Further, in a molecule, with the R3The group of expression At least one is the aryl or the aralkyl, preferably phenyl.
In addition, x, y and z are respectively to meet 0.01≤x≤0.5,0.01≤y≤0.4,0.1≤z≤0.9 and x+y in formula The number of+z=1, the preferably number of satisfaction 0.05≤x≤0.45,0.05≤y≤0.4,0.2≤z≤0.8 and x+y+z=1, or Person is the number for meeting 0.05≤x≤0.4,0.1≤y≤0.4,0.3≤z≤0.8 and x+y+z=1.This is because when x is upper When stating the lower limit of range or more, hardening thing is difficult to generate sticky sense, be on the other hand because, when x be above range the upper limit with When lower, the intensity of hardening thing is good.In addition, this is because when y be above range lower limit more than when, the elongation of hardening thing It improves, is on the other hand because when below the upper limit that y is above range, the mechanical property of hardening thing is improved.In addition, this is Because when z be above range lower limit more than when, the refractive index of hardening thing is good, barrier properties for gases is good, be on the other hand because For when below the upper limit that z is above range, the mechanical property of hardening thing is improved.
(A) ingredient can be a kind of organopolysiloxane, or may be organopolysiloxane mixing of more than two kinds Object.(A) in the case that ingredient is at least two kinds of organopolysiloxanes, as long as mixture is to be indicated with above-mentioned averaged unit formula Substance.As the mixture of such organopolysiloxane, can enumerate by with formula: R1 3SiO1/2The siloxane unit of expression, With formula: R2 2SiO2/2The siloxane unit of expression and with formula: R3SiO3/2The organopolysiloxane that the siloxane unit of expression is constituted, And by with formula: R1 3SiO1/2The siloxane unit of expression, with formula: R2 2SiO2/2The siloxane unit of expression and with formula: R3SiO3/2 The mixture for the organopolysiloxane that the siloxane unit of expression is constituted；By with formula: R1 3SiO1/2The siloxane unit of expression, with Formula: R2 2SiO2/2The siloxane unit of expression and with formula: R3SiO3/2The organopolysiloxane that the siloxane unit of expression is constituted, with And by with formula: R1 3SiO1/2The siloxane unit of expression and with formula: R3SiO3/2Organic poly- silicon that the siloxane unit of expression is constituted The mixture of oxygen alkane；By with formula: R1 3SiO1/2The siloxane unit of expression, with formula: R2 2SiO2/2The siloxane unit of expression and with Formula: R3SiO3/2The organopolysiloxane that the siloxane unit of expression is constituted, and by with R2 2SiO2/2The siloxane unit of expression With with formula: R3SiO3/2The mixture for the organopolysiloxane that the siloxane unit of expression is constituted.Further, this hair is not being damaged In the range of bright purpose, it can have in (A) ingredient with formula: SiO4/2The siloxane unit of expression.Further, it is not damaging In the range of the object of the invention, can be bonded in the silicon atom in (A) ingredient the alkoxies such as methoxyl group, ethyoxyl, propoxyl group or Hydroxyl.
The method of the organopolysiloxane of preparation (A) ingredient is not limited, it can be mentioned, for example following methods: will be with logical Formula:
R3SiX3
The silane (I) of expression, with general formula:
R2 2SiY2
The silane (II-1) of expression and with general formula:
R1 3SiOSiR1 3
The disiloxane (III-1) of expression in the presence of acids and bases, is hydrolyzed, condensation reaction.
Silane (I) is for importing into organopolysiloxane obtained with formula: R3SiO3/2The siloxane unit of expression Raw material.In formula, R3For carbon number be 1~12 alkyl, carbon number be 6~20 aryl or carbon number be 7~20 aralkyl, Group similar to the above can be illustrated.In addition, Y is alkoxy, acyloxy, halogen atom or hydroxyl in formula.First can specifically be illustrated The alkoxies such as oxygroup, ethyoxyl, propoxyl group；The acyloxy such as acetoxyl group；The halogen atoms such as chlorine atom, bromine atom.
As the silane (I), phenyltrimethoxysila,e, naphthalene trimethoxy silane, anthryl trimethoxy silicon can be illustrated Alkane, phenanthryl trimethoxy silane, pyrenyl trimethoxy silane, phenyl triethoxysilane, naphthyl-triethyoxy silicane alkane, anthryl three Ethoxysilane, phenanthryl triethoxysilane, pyrenyl triethoxysilane, methyltrimethoxysilane, ethyl trimethoxy silicon The alkoxy silanes such as alkane, methyltriethoxysilane；Phenyl triacetoxysilane, naphthalene triacetoxysilane, anthryl three Acetoxylsilane, phenanthryl triacetoxysilane, pyrenyl triacetoxysilane, methyl triacetoxysilane, ethyl three The acyloxy silanes such as acetoxylsilane；Phenyl trichlorosilane, naphthalene trichlorosilane, anthryl trichlorosilane, phenanthryl trichlorosilane, The halogenated silanes such as pyrenyl trichlorosilane, methyl trichlorosilane, ethyl trichlorosilane；Phenyl ortho-siliformic acid, naphthalene trihydroxy silicon Alkane, anthryl ortho-siliformic acid, phenanthryl ortho-siliformic acid, pyrenyl ortho-siliformic acid, methyl ortho-siliformic acid, ethyl ortho-siliformic acid Equal silicols.
In addition, silane (II-1) is for importing into organopolysiloxane obtained with formula: R2 2SiO2/2The silicon of expression The raw material of oxygen alkane unit.In formula, R2For identical or different carbon number be 1~12 alkyl or carbon number be 2~12 alkenyl, Group similar to the above can be illustrated.In addition, in formula, Y is alkoxy, acyloxy, halogen atom or hydroxyl, can illustrate with it is above-mentioned same The group of sample.
As the silane (II-1), dimethyldimethoxysil,ne, diethyldimethoxysilane, dipropyl two can be illustrated Methoxy silane, Methylethyl dimethoxysilane, methylvinyldimethoxysilane, dimethyl diethoxysilane, two Ethyl diethoxy silane, dipropyl diethoxy silane, Methylethyl diethoxy silane, methyl ethylene diethoxy silicon The dialkoxy silicanes such as alkane；Dimethyl 2 acetoxyl group silane, Methylethyl diacetoxy silane, methyl ethylene diacetyl The diacetoxies silane such as oxysilane；Dimethyldichlorosilane, diethyl dichlorosilane, dipropyl dichlorosilane, methyl second The dihalide halosilanes such as base dichlorosilane, methylvinyldichlorosilane；Dimethyldihydroxysilane, diethyl dihydroxy base silane, The dihydroxies base silanes such as dipropyl dihydroxy base silane, Methylethyl dihydroxy base silane, methyl ethylene dihydroxy base silane.
In addition, disiloxane (III-1) is for importing into organopolysiloxane obtained with formula: R1 3SiO1/2Table The raw material of the siloxane unit shown.In formula, R1For identical or different carbon number be 1~12 alkyl, carbon number be 2~12 alkene The aralkyl that the aryl or carbon number that base, carbon number are 6~20 are 7~20, can illustrate group similar to the above.
As the disiloxane (III-1), 1,1,1,3,3,3- hexamethyldisiloxane, 1,3- divinyl-can be illustrated 1,1,3,3- tetramethyl disiloxane, 1,3- divinyl -1,1,3,3- tetraethyl disiloxane, 1,1,3,3- tetravinyl - 1,3- dimethyldisiloxane, six vinyl disiloxane of 1,1,1,3,3,3-, 1,3- diphenyl -1,3- divinyl -1,3- Dimethyldisiloxane, 1,1,3,3- tetraphenyl -1,3- divinyl disiloxane.
In the above-mentioned methods, can replace silane (II-1) or on the basis of silane (II-1) use with general formula:
(R2 2SiO)p
The annular siloxane (II-2) of expression.In formula, R2The alkyl or carbon for being 1~12 for identical or different carbon number The alkenyl that number is 2~12, can illustrate group similar to the above.In addition, in formula, integer that p is 3 or more.
As the annular siloxane (II-2), 1,1,3,3,5,5,7,7- octamethylcy-clotetrasiloxane, 1 can be illustrated, 3,5, 7- tetravinyl -1,3,5,7- tetramethyl-ring tetrasiloxane, 1,1,3,3,5,5,7,7- octaethyl cyclotetrasiloxane.
In addition, in the above-mentioned methods, can replace silane (II-1) and annular siloxane (II-2) or in silane (II- 1) and/or on the basis of annular siloxane (II-2), use is with general formula:
HO(R2 2SiO)qH
The straight-chain siloxanes (II-3) of expression.In formula, R2For identical or different carbon number be 1~12 alkyl or The alkenyl that carbon number is 2~12, can illustrate group similar to the above.In addition, in formula, integer that q is 2 or more.
As the straight-chain siloxanes (II-3), two end of strand can be illustrated by the dimethyl-silicon of capped silanol groups Methyl vinyl silicone oligomer by capped silanol groups of oxygen alkane oligomer, two end of strand, two end of strand By the di-ethyl siloxane oligomer of capped silanol groups, two end of strand by capped silanol groups dipropyl silicon oxygen Alkane oligomer.
In addition, in the above-mentioned methods, can replace disiloxane (III-1) or on the basis of disiloxane (III-1) Upper use is with general formula:
R1 3SiY
The silane (III-2) of expression.In formula, R1For identical or different carbon number be 1~12 alkyl, carbon number be 2~12 Alkenyl, carbon number be 6~20 aryl or carbon number be 7~20 aralkyl, group similar to the above can be illustrated.In addition, In formula, Y is alkoxy, acyloxy, halogen atom or hydroxyl, can illustrate group similar to the above.
As such silane (III-2), trimethylmethoxysilane, triethyl group methoxy silane, dimethyl can be illustrated Vinyl methoxy silane, diethyl vinyl methoxy silane, Vinyldimethylethoxysilane, diethyl vinyl second Oxysilane, divinylmethyl methoxy silane, trivinyl methoxy silane, methyl phenyl vinyl methoxy silane, The alkoxy silanes such as methyldiphenyl methoxylsilane, diphenylethlene methoxylsilane；Trimethylacetoxysilane, two Methyl ethylene acetoxylsilane, diethyl vinyl alkoxysilicone, divinylmethyl acetoxylsilane, three second Alkenyl acetoxylsilane, methyl phenyl vinyl acetoxylsilane, methyldiphenyl base acetoxylsilane, diphenylethlene The acyloxy silanes such as base acetoxylsilane；Trim,ethylchlorosilane, dimethyl vinyl chlorosilane, diethyl vinyl chloride silicon Alkane, divinylmethyl chlorosilane, trivinyl chlorosilane, methyl phenyl vinyl chlorosilane, methyldiphenyl base chlorosilane etc. Halogenated silanes；Trimethyl silanol, dimethyl ethenyl silicol, diethyl vinyl hydroxy silane, divinyl first The hydroxyls silicon such as base silicol, trivinyl silicol, methyl phenyl vinyl silicol, methyldiphenylhydroxysilane Alkane.
In addition, in the above-mentioned methods, can according to need and be used in importing with formula: SiO4/2The siloxane unit of expression Silane or siloxane oligomer are reacted with organopolysiloxane obtained.As such silane, tetramethoxy-silicane can be illustrated The alkoxy silanes such as alkane, tetraethoxysilane；The acyloxy silanes such as four acetoxylsilanes；The halogenated silanes such as tetrachloro silicane.Separately Outside, as siloxane oligomer, the partial hydrolystate of tetramethoxy-silicane, the partial hydrolystate of tetraethoxysilane can be illustrated.
In the above-mentioned methods, which is characterized in that by silane (I), silane (II-1) and disiloxane (III-1) or generation Cyclic annular disiloxane (II-2) and/or straight-chain siloxanes (II- for silane (II-1) or on the basis of silane (II-1) 3) disiloxane (III-1) or silane (III-2) on the basis of disiloxane (III-1), are further replaced and into one Other as needed silane of step or siloxane oligomer be hydrolyzed in the presence of acids and bases, condensation reaction.It needs to illustrate , at least one kind of aryl or carbon number for being 6~20 with carbon number of silane (I) used is 7~20 in the above preparation method Aralkyl, silane (II-1), cyclic annular disiloxane (II-2), straight-chain siloxanes (II-3), disiloxane (III-1) and At least one kind of alkenyl for being 2~12 with carbon number of silane (III-2).
In addition, as acid used in the above method, can illustrate hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, Polyphosphoric acid, polybasic carboxylic acid, trifluoromethayl sulfonic acid, ion exchange resin.In addition, can be illustrated as alkali used in the above method The inorganic bases such as potassium hydroxide, sodium hydroxide；Triethylamine, diethylamide, monoethanolamine, diethanol amine, triethanolamine, ammonium hydroxide, The organo-alkali compounds such as tetramethylammonium hydroxide, the alkoxy silane with amino, aminopropane trimethoxy silane.
In addition, in the above-mentioned methods, organic solvent can be used.As the organic solvent, ethers, ketone, second can be illustrated Esters of gallic acid, aromatic series or aliphatic hydrocarbon, gamma-butyrolacton and their mixtures of more than two kinds.It, can as preferred organic solvent Illustrate propylene glycol monomethyl ether, propylene glycol methyl ether acetate, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, third The tertiary butyl ether of glycol list, gamma-butyrolacton, toluene, dimethylbenzene.
In the above-mentioned methods, in order to promote hydrolysis, condensation reaction, the mixed liquor of water or water and alcohol is preferably added.As this Alcohol, preferably methanol, ethyl alcohol.In addition, the reaction promotes its process using heating, using organic solvent, preferably It is reacted with its reflux temperature.
(B) ingredient is the organopolysiloxane of the straight-chain in a molecule at least two alkenyl.As in (B) ingredient Alkenyl, can illustrate vinyl, allyl, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decene base, Undecenyl, dodecenyl succinic, preferably vinyl.In addition, as other than the alkenyl in (B) ingredient and silicon atom bonding Group, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, 12 can be illustrated The alkyl such as alkyl；The aryl such as phenyl, tolyl, xylyl, naphthalene, anthryl, phenanthryl, pyrenyl；Benzyl, phenethyl, naphthylethyl, The aralkyl such as naphthalene propyl, anthracene ethyl, luxuriant and rich with fragrance ethyl, pyrene ethyl；And it is partly or entirely taken with halogen atoms such as chlorine atom, bromine atoms For the group with the hydrogen atom of these group bondings, preferably methyl, phenyl.Do not have for viscosity of (B) ingredient at 25 DEG C There are a restriction, preferably 10~10, in the range of 000,000mPas, in the range of 10~1,000,000mPas or 10 In the range of~100,000mPas.This is because when more than the lower limit that the viscosity of (B) ingredient is above range, acquisition The mechanical property of hardening thing improves, and is on the other hand because when below the upper limit that the viscosity of (B) ingredient is above range, obtaining The processing operation of the composition obtained improves.
As (B) ingredient, the organopolysiloxane that can be listed below.It should be noted that Me, Vi, Ph distinguish table in formula Show that methyl, vinyl, phenyl, m and m ' are respectively 1 or more integer.
ViMe2SiO(Me2SiO)mSiMe2Vi
ViPhMeSiO(Me2SiO)mSiMePhVi
ViPh2SiO(Me2SiO)mSiPh2Vi
ViMe2SiO(Me2SiO)m(Ph2SiO)m’SiMe2Vi
ViPhMeSiO(Me2SiO)m(Ph2SiO)m’SiPhMeVi
ViPh2SiO(Me2SiO)m(Ph2SiO)m’SiPh2Vi
ViMe2SiO(MePhSiO)mSiMe2Vi
MePhViSiO(MePhSiO)mSiMePhVi
Ph2ViSiO(MePhSiO)mSiPh2Vi
ViMe2SiO(Ph2SiO)m(PhMeSiO)m’SiMe2Vi
ViPhMeSiO(Ph2SiO)m(PhMeSiO)m’SiPhMeVi
ViPh2SiO(Ph2SiO)m(PhMeSiO)m’SiPh2Vi
In the present compositions, relative to 100 mass parts of (A) ingredient, the content of (B) ingredient is the model of 0.1~60 mass parts In enclosing, in the range of preferably 0.1~50 mass parts or in the range of 0.1~40 mass parts.This is because when (B) ingredient When content is the lower limit of above range or more, hardening thing flexibility can be assigned, is on the other hand because of when containing for (B) ingredient When amount is the upper limit of above range or less, the mechanical property of the hardening thing of acquisition is good.
(C) ingredient is the organopolysiloxane of the hydrogen atom at least two and silicon atom bonding in a molecule.As (C) molecular structure of ingredient can illustrate for example: straight-chain, a part have straight-chain, branched, ring-type and the branch of branch Shape.Preferably straight-chain, dendroid with branch of straight-chain, a part.For the hydrogen with silicon atom bonding in (C) ingredient The bonding position of atom does not limit, and it can be mentioned, for example molecule chain end and/or strand side chains.In addition, as in (C) ingredient Water element atom other than the group with silicon atom bonding, can illustrate methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, The alkyl such as octyl, nonyl, decyl, undecyl, dodecyl；Benzyl, phenethyl, naphthylethyl, naphthalene propyl, anthracene ethyl, luxuriant and rich with fragrance second The aralkyl such as base, pyrene ethyl；The halogenated alkyls such as chloromethyl, 3- chloropropyl, 3,3,3- trifluoro propyl；3- glycidoxypropyl group, The glycidoxyalkyls such as 4- glycidoxy butyl；2- (3,4- epoxycyclohexyl) ethyl, 3- (3,4- epoxycyclohexyl) third The epoxycyclohexyls alkyl such as base.In addition, viscosity of (C) ingredient at 25 DEG C is not limited, preferably 1~10, In the range of 000mPas, or in the range of 1~1,000mPas.
As (C) ingredient, 1,1,3,3- tetramethyl disiloxane, 1,3,5,7- tetramethyl-ring tetrasiloxanes, three can be illustrated (dimethylhydrogensiloxy) methyl-monosilane, three (dimethylhydrogensiloxy) phenyl silanes, 1- (3- glycidoxy third Base) -1,3,5,7- tetramethyl-ring tetrasiloxane, 1,5- bis- (3- glycidoxypropyl group) -1,3,5,7- tetramethyl cyclotetrasiloxane silicon oxygen Alkane, 1- (3- glycidoxypropyl group) -5- trimethoxysilylethylgroup group -1,3,5,7- tetramethyl-ring tetrasiloxane, molecule Trimethyl silyl is used with the methylhydrogenpolysi,oxane of trimethylsiloxy sealing end, two end of strand in two end of chain Dimethylhydrogensiloxy is used in dimethyl siloxane/methylhydrogensiloxacopolymer copolymer of oxygroup sealing end, two end of strand Diphenyl siloxane that the dimethyl polysiloxane of sealing end, two end of strand are blocked with dimethylhydrogensiloxy, point Two end of subchain is with dimethyl siloxane/methylhydrogensiloxacopolymer copolymer of dimethylhydrogensiloxy sealing end, strand Two ends are with methyl hydrogen siloxane/diphenylsiloxane copolymer of trimethylsiloxy sealing end, two end of strand Methyl hydrogen siloxane/diphenyl siloxane/the dimethylsiloxane copolymer, trimethoxy blocked with trimethylsiloxy The hydrolytic condensate of base silane, by (CH3)2HSiO1/2Unit and SiO4/2Unit constitute copolymer, by (CH3)2HSiO1/2It is single Member, SiO4/2Unit and (C6H5)SiO3/2The copolymer and their mixture of more than two kinds that unit is constituted.
Further, as (C) ingredient, following organosiloxane can also be illustrated.It should be noted that in formula, Me, Ph, Naph respectively indicates methyl, phenyl, naphthalene, and n and n ' are respectively 1 or more integer, and i, j, k and l are respectively to meet 0 < i < 1,0 < j < 1, the number of 0 < k < 1,0 < 1 < 1 and i+j+k+l=1.
HMe2SiO(Ph2SiO)nSiMe2H
HMePhSiO(Ph2SiO)nSiMePhH
HMePhNaphSiO(Ph2SiO)nSiMeNaphH
HMePhSiO(Ph2SiO)n(MePhSiO)n’SiMePhH
HMePhSiO(Ph2SiO)n(Me2SiO)n’SiMePhH
(HMe2SiO1/2)i(PhSiO3/2)j
(HMePhSiO1/2)i(PhSiO3/2)j
(HMePhSiO1/2)i(NaphSiO3/2)j
(HMe2SiO1/2)i(NaphSiO3/2)j
(HMePhSiO1/2)i(HMe2SiO1/2)j(PhSiO3/2)k
(HMe2SiO1/2)i(SiO4/2)j
(HMe2SiO1/2)i(SiO4/2)j(PhSiO3/2)k
(HMePhSiO1/2)i(SiO4/2)j(PhSiO3/2)k
(HMe2SiO1/2)i(SiO4/2)j(NaphSiO3/2)k
(HMePhSiO1/2)i(SiO4/2)j(NaphSiO3/2)k
(HMePhSiO1/2)i(HMe2SiO1/2)j(NaphSiO3/2)k
(HMePhSiO1/2)i(HMe2SiO1/2)j(SiO4/2)k(NaphSiO3/2)1
(HMePhSiO1/2)i(HMe2SiO1/2)j(SiO4/2)k(PhSiO3/2)1
In the present compositions, for the content of (C) ingredient, relative to alkenyl contained in (A) ingredient and (B) ingredient Total 1 mole, it is excellent in the range of being 0.1~10 mole with the content of the hydrogen atom of silicon atom bonding contained in this ingredient It is selected as in the range of 0.5~5 mole.This is because when more than the lower limit that the content of (C) ingredient is above range, acquisition Composition is sufficiently hardened, be on the other hand because, when the content of (C) ingredient be above range the upper limit below when, acquisition it is hard The heat resistance of compound increases, and then the reliability of the optical semiconductor device made using this composition is increased.
(D) ingredient is the hydrosilylation reactions catalyst for promoting this composition to harden.It, can as (D) ingredient Illustrate platinum-type catalyst, rhodium class catalyst, palladium class catalyst, preferably platinum-type catalyst.As the platinum-type catalyst, can illustrate Platinum attritive powder, platinum black, platinum load the alkene of silicon attritive powder, platinum load type active carbon, chloroplatinic acid, the alcoholic solution of chloroplatinic acid, platinum The platinum-like compounds such as alkenyl siloxane complex compound of complex compound, platinum.
In the present compositions, the content of (D) ingredient is to promote the amount of this composition hardening, specifically, relative to this group Object is closed, the metallic atom in the catalyst is calculated as the amount in the range of 0.01~1,000ppm with mass unit.At this moment because, when (D) content of ingredient be above range lower limit more than when, the hardening of the composition of acquisition sufficiently carries out, be on the other hand because For when below the upper limit that the content of (D) ingredient is above range, the hardening thing of acquisition is difficult to colour.
For this composition, in order to extend service life at normal temperature, improve storage stability, it can also contain (E) hydrosilylation reactions inhibitor.As (E) ingredient, can illustrate 1- hexamethylene acetylene -1- alcohol, 2- methyl -3- butyne-2-alcohol, The alkynols such as 3,5- dimethyl -1- hexin -3- alcohol, 2- phenyl -3- butyne-2-alcohol；3- methyl-pirylene, 3,5- diformazan The yne compounds such as base -3- hexene -1- alkynes；1,3,5,7- tetramethyl -1,3,5,7- tetravinyl cyclotetrasiloxane, 1,3,5,7- The methyl alkenyl siloxane oligomer such as four hexenyl cyclotetrasiloxane of tetramethyl -1,3,5,7-；Bis- (the 3- methyl-1s-fourth of dimethyl Alkynes-3- oxygen) alkoxy silanes, triallyl isocyanide urea such as silane, bis- (3- methyl-1-butine-3- oxygen) silane of methyl ethylene Acid esters compound.
The content of (E) ingredient is not limited, adds up to 100 mass parts relative to above-mentioned (A) ingredient~(C) ingredient, In the range of preferably 0.01~3 mass parts, or in the range of 0.01~1 mass parts.This is because when (E) ingredient Content be above range lower limit more than when, this composition have service life appropriate, be on the other hand because, when (E) at When the content divided is the upper limit of above range or less, this composition has operability appropriate.
It further,, can in order to further increase the cementability of the substrate for contacting in hardening for this composition To contain (F) adhesion promoters.As (F) ingredient, there is the alkoxy of at least one and silicon atom bonding in a preferably molecule Organo-silicon compound.As the alkoxy, methoxyl group, ethyoxyl, propoxyl group, butoxy and methoxy ethoxy can be illustrated, it is excellent It is selected as methoxyl group, ethyoxyl.In addition, as in the organo-silicon compound with the group other than the alkoxy of silicon atom bonding, can Illustrate the alkane such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl Base；Vinyl, allyl, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decene base, undecenyl, The alkenyls such as dodecenyl succinic；The aryl such as phenyl, tolyl, xylyl, naphthalene, anthryl, phenanthryl, pyrenyl；Benzyl, phenethyl, The aralkyl such as naphthylethyl, naphthalene propyl, anthracene ethyl, luxuriant and rich with fragrance ethyl, pyrene ethyl；And with the halogen atoms such as chlorine atom, bromine atom part Or all instead of the group of the hydrogen atom with these group bondings；3- glycidoxypropyl group, 4- glycidoxy butyl etc. Glycidoxyalkyl；The epoxycyclohexyls alkane such as 2- (3,4- epoxycyclohexyl) ethyl, 3- (3,4-epoxycyclohexyl) propyl Base；The oxiranylalkyl groups such as 4- oxiranylbutyl and 8- epoxy ethyl octyl；The propylene such as 3- methacryloxypropyl Acyloxyallcyl；And isocyanate group, isocyanuric acid base, hydrogen atom.
The organo-silicon compound preferably have and can occur with the alkenyl in this composition or with the hydrogen atom of silicon atom bonding The group of reaction, specifically, it is preferable that having the hydrogen atom or alkenyl with silicon atom bonding.Molecule knot as the silicon compound Structure can illustrate straight-chain, a part has straight-chain, branched, ring-type, netted, the especially preferred straight-chain, branch of branch It is shape, netted.As such organo-silicon compound, 3- glycidoxypropyltrime,hoxysilane, 2- (3,4- epoxies can be illustrated Cyclohexyl) silane compounds such as ethyl trimethoxy silane, 3- methyl allyl acyloxypropyl trimethoxysilane；Divide in one molecule Not Ju You at least one and silicon atom bonding alkenyl or with the hydrogen atom of silicon atom bonding and with the alcoxyl of silicon atom bonding The silicone compounds of base, the silane compound of alkoxy at least one and silicon atom bonding or silicone compounds and Be respectively provided in one molecule at least one and silicon atom bonding hydroxyl and with the silicone compounds of the alkenyl of silicon atom bonding Mixture, with averaged unit formula:
[chemical formula 1]
(in formula, r, s and t are respectively positive number)
The silicone compounds of expression, with averaged unit formula:
[chemical formula 2]
(in formula, r, s, t and u are respectively positive number)
The silicone compounds of expression.
The content of (F) ingredient is not limited, adds up to 100 mass parts relative to above-mentioned (A) ingredient~(C) ingredient, In the range of preferably 0.1~5 mass parts, or in the range of 1~5 mass parts.This is because when the content of (F) ingredient When to be more than the lower limit of above range, adhesiveness is good, is on the other hand because of when the content of (F) ingredient is above range When below the upper limit, storage stability is good.
Further, for this composition, in order to convert the emission wavelength from optical semiconductor, can contain (G) fluorophor.As (G) ingredient, for example, can enumerate extensively be used in light emitting diode (LED) by oxide-based fluorescence The Huang of the compositions such as body, nitrogen oxidation species fluorophor, nitride based phosphor, sulfide based phosphor, oxysulfide class fluorophor Color, red, green and blue-light-emitting fluorescent material.As oxynitride based phosphor, can illustrate: yttrium, aluminium comprising cerium ion, YAG class green~yellow luminescent phosphor, the terbium comprising cerium ion, aluminium, the TAG class of Garnet of Garnet are Yellow luminous Fluorophor and silicates green~yellow luminescent phosphor comprising cerium and europium ion.As nitrogen oxidation species fluorophor, It can illustrate: silicon aluminum oxygen nitrogen type of red~green-emitting phosphor body of silicon, aluminium, oxygen, nitrogen class comprising europium ion.As nitride-based Fluorophor can illustrate: CASN (CaAlSiN3) type of red light-emitting fluophor of calcium, strontium, aluminium, silicon, nitrogen class comprising europium ion.Make It for sulfide based phosphor, can illustrate: comprising copper ion or aluminum ions ZnS class green-emitting phosphor body.As oxysulfide Class fluorophor can illustrate: the Y comprising europium ion2O2S type of red light-emitting fluophor.Can combine two or more these fluorophor into It exercises and uses.
The average grain diameter of (G) ingredient is not limited, in the range of preferably 1~50 μm, or is 5~20 μm of model In enclosing.This is because when more than the lower limit that the average grain diameter of (G) ingredient is above range, in viscosity when can inhibit mixing It rises, is on the other hand because when below the upper limit that the average grain diameter of (G) ingredient is above range, photopermeability is good.
Relative to above-mentioned (A) ingredient~(C) ingredient total amount, the content of (G) ingredient is the model of 0.1~70 mass percent In enclosing, in the range of preferably 1~70 mass percent or in the range of 5~70 mass percents.This is because as (G) When the content of ingredient is the lower limit of above range or more, wavelength conversion can be effectively performed, be on the other hand because of as (G) When the content of ingredient is the upper limit of above range or less, the operability of the composition of acquisition increases.
Further, in order to sufficiently inhibit electrode, the base in the optical semiconductor device as caused by the sulfurous gas in air The silver-plated discoloration of plate, this composition can be containing selected from by selected from by Al, Ag, Cu, Fe, Sb, Si, Sn, Ti, Zr and rare earth The oxide of at least one of the group of element composition element carries out the zinc oxide attritive powder of surface covering, not have alkenyl The zinc oxide attritive powder that is surface-treated of organo-silicon compound and zinc carbonate hydrate attritive powder composition group in And average grain diameter be 0.1nm~5 μm at least one attritive powder.
In the zinc oxide attritive powder for carrying out surface covering with oxide, as rare earth element, it can illustrate: yttrium, cerium, europium. The oxide on the surface as zinc oxide attritive powder can illustrate Al2O3、AgO、Ag2O、Ag2O3、CuO、Cu2O、FeO、Fe2O3、 Fe3O4、Sb2O3、SiO2、SnO2、Ti2O3、TiO2、Ti3O5、ZrO2、Y2O3、CeO2、Eu2O3And two or more of these oxides Mixture.
The content of the powder is not limited, is preferably 1ppm~10% in terms of mass unit relative to this composition In the range of amount or the amount in the range of 1ppm~5%.This is because when the powder content be above range lower limit with When upper, it can sufficiently inhibit the silver-plated discoloration of the electrode or substrate in the optical semiconductor device as caused by sulfurous gas, separately It on the one hand is because when below the upper limit that the content of the powder is above range, the flowing of the composition of acquisition will not be damaged Property.
In addition, for this composition, from the light as caused by the sulfurous gas in air half can be further suppressed From the aspect of the silver-plated discoloration of electrode or substrate in conductor device, triazole class compounds can be contained.As triazole type Compound, can example 1H-1,2,3- triazoles, 2H-1,2,3- triazoles, 1H-1,2,4- triazoles, 4H-1,2,4- triazoles, 2- (2 '-hydroxyls Base -5 '-aminomethyl phenyl) benzotriazole, 1H-1,2,3- triazole, 2H-1,2,3- triazole, 1H-1,2,4- triazole, 4H-1,2,4- tri- Azoles, benzotriazole, azimido-toluene, carboxyl benzotriazole, 1H- benzotriazole -5- carboxylate methyl ester, 3- amino -1,2,4- triazole, 4- amino -1,2,4- triazole, 5- amino -1,2,4- triazole, 3- sulfydryl -1,2,4- triazole, chlorobenzotriazole, nitro benzo three Azoles, amino benzotriazole, cyclohexanone [1,2-d] triazole, 4,5,6,7- tetrahydroxy azimido-toluene, I-hydroxybenzotriazole, second Base benzotriazole, naphthalene triazole, 1-N, N- bis- (2- ethylhexyl)-[(1,2,4- triazol-1-yl) methyl] amine, [N, N- are bis- by 1- (2- ethylhexyl) amino methyl] benzotriazole, 1- [bis- (2- ethylhexyl) amino methyls of N, N-] azimido-toluene, 1- [N, Bis- (2- ethylhexyl) amino methyls of N-] carboxyl benzotriazole, 1- [bis- (2- the ethoxy)-amino methyls of N, N-] benzotriazole, 1- [bis- (2- the hydroxyethyl)-amino methyls of N, N-] azimido-toluene, 1- [bis- (2- the ethoxy)-amino methyls of N, N-] carboxyl benzene And triazole, 1- [bis- (2- hydroxypropyl) amino methyls of N, N-] carboxyl benzotriazole, 1- [bis- (1- butyl) amino methyls of N, N-] carboxylic Base benzotriazole, 1- [bis- (1- octyl) amino methyls of N, N-] carboxyl benzotriazole, 1- (2 ', 3 '-bis-hydroxy propyl) benzo three Azoles, 1- (2 ', 3 '-two-carboxy ethyl) benzotriazole, 2- (2 '-hydroxyls -3 ', 5 '-di-tert-butyl-phenyls) benzotriazole, 2- (2 '-hydroxyls -3 ', 5 '-aminophenyls) benzotriazole, 2- (2 '--4 '-octyloxyphenyl of hydroxyl) benzotriazole, 2- (2 '-hydroxyls Base -5 '-tert-butyl-phenyl) benzotriazole, I-hydroxybenzotriazole -6- carboxylic acid, 1- oleoylbenzotriazole, 1,2,4- triazole -3- Alcohol, 5- amino -3- sulfydryl -1,2,4- triazole, 5- amino -1,2,4- triazole -3- formic acid, 1,2,4- triazole -3- formamide, 4- ammonia Base urazole, 1,2,4- triazole -5- ketone.The content of the triazole class compounds is not particularly limited, in the present compositions, with matter Amount unit is calculated as the amount in the range of 0.01ppm~3%, the preferably amount in the range of 0.1ppm~1%.
Further, for this composition, as long as not damaging the purpose of the present invention, it is used as any other ingredient, it can To contain the inanimate matters fillers such as silica, glass, aluminium oxide, zinc oxide；The organic resins such as polymethacrylate resin Attritive powder；Heat-resistant agent, dyestuff, pigment, anti-flammability imparting agent, solvent etc..
Viscosity for this composition at 25 DEG C does not limit, in the range of preferably 100~500,000mPas, or In the range of person is 100~100,000mPas.This such composition can harden at room temperature or after being heated, in order to Quick-hardening is preferably heated.As the heating temperature, in the range of preferably 50~200 DEG C.
Then, hardening thing of the invention is described in detail.
Hardening thing of the invention is characterized in that, above-mentioned hardenability silicon composition is hardened.For hardening thing Shape is not particularly limited, and it can be mentioned, for example flakes, film-form.In addition, the hardening thing can partly lead to seal or covering light The state of volume elements part etc..
Then, optical semiconductor device of the invention is described in detail.
Optical semiconductor device of the invention is characterized in that, optical semiconductor is utilized above-mentioned hardenability silicon composition Hardened mass seals or cover.As such optical semiconductor device of the invention, can illustrate light emitting diode (LED), Photoelectrical coupler, CCD.In addition, light emitting diode (LED) chip, solid-state imager can be enumerated as optical semiconductor.
The sectional view of the monomer surface mount type LED of an example of optical semiconductor device of the invention is as shown in Figure 1.In Fig. 1 1 chip of optical semiconductor is welded on lead frame 2 by the LED of display, and using bonding wire 4 by the optical semiconductor 1 with Lead frame 3 carries out lead welding.It is provided with frame part 5 around the optical semiconductor 1, the light of the inside of the frame part 5 Semiconductor element 1 is sealed by the hardening thing 6 of hardenability silicon composition of the invention.
As the method for manufacturing surface mounting LED shown in FIG. 1, can illustrate following methods: chip welds on lead frame 2 Optical semiconductor 1 is connect, the semiconductor element 1 and lead frame 3 are welded using 4 lead of bonding wire of gold system, then, are being set to Hardenability silicon composition of the present invention is filled in the inside of frame part 5 around optical semiconductor 1, then by 50~200 DEG C It is heated and makes its hardening.
Embodiment
Hereinafter, passing through the embodiment hardenability silicon composition that the present invention will be described in detail, its hardening thing and photosemiconductor dress It sets.It should be noted that value when viscosity in embodiment is 25 DEG C, in formula, Me, Vi, Ph and Ep respectively indicate methyl, Vinyl, phenyl, 3- glycidoxypropyl group.In addition, the characteristic of hardenability silicon composition and its hardening thing is measured as follows, by this As a result shown in table 1.
[refractive index of hardenability silicon composition]
Refractive index of the hardenability silicon composition at 25 DEG C is measured using Abbe refractometer.It should be noted that The light source of 589nm is used in measurement.
[dispersibility of fluorophor]
Relative to 100 mass parts of hardenability silicon composition, dentistry blender mixing YAG class fluorophor (INTEMATIX is utilized The MX311 (B) of company's manufacture) 3 mass parts conduct (G) ingredient.Later, the hardenability silicon composition containing fluorophor is coated on On glass plate, is heated 1 hour in 150 DEG C of baking oven, thus make its hardening.Visually observe the fluorescence in hardening thing obtained The dispersity of body will evaluate as follows its result.
Zero: fluorophor is evenly dispersed.
Δ: a part cohesion of fluorophor.
×: most of cohesion of fluorophor.
[cracking]
Relative to 100 mass parts of hardenability silicon composition, dentistry blender mixing YAG class fluorophor (INTEMATIX is utilized The MX311 (B) of company's manufacture) 50 mass parts conduct (G) ingredient, prepare the hardenability silicon composition containing fluorophor.
Then, the hardenability silicon composition using this containing fluorophor, is made optical semiconductor device shown in FIG. 1.It needs Bright, hardenability silicon composition heats 3 hours at 150 DEG C, makes its hardening.Optical semiconductor device obtained is applied The charge of 520mA makes its bright light under conditions of 85 DEG C, humidity 85%, carries out endurance test.Electronic display is used after 400 hours Micro mirror confirms the appearance of sealing material, evaluates its result as follows.
Zero: not observing crackle on sealing material.
Δ: crackle is observed on a part of sealing material.
×: crackle is all observed on all sealing materials.
[synthesis example 1]
With blender, reflux condenser, thermometer four-hole boiling flask in, put into 1,3- divinyl -1,1,3,3- tetra- Tetramethyldisiloxane 70.6g (0.38mol), octamethylcy-clotetrasiloxane 56.2g (0.19mol), phenyltrimethoxysila,e 450.5g (2.27mol) and trifluoromethayl sulfonic acid 0.35g, under stiring, 30 minutes used times dropwise addition water 122.8g (6.81mol).After completion of dropwise addition, 85 DEG C are heated to, the methanol of production is distilled off.Then, toluene 105g and 30 matter are put into The potassium hydroxide aqueous solution 2.8g for measuring percentage, makes water azeotropic dehydration.Later, it after 125 DEG C are kept for 6 hours, is cooled to room temperature, It is neutralized with acetic acid 0.9g.After being filtered to the salt of generation, the heating decompression removal low boiling from clear solution obtained Point object, prepare colorless and transparent and number-average molecular weight for Isosorbide-5-Nitrae 00, with averaged unit formula:
(ViMe2SiO1/2)0.20(Me2SiO2/2)0.20(PhSiO3/2)0.60
Organopolysiloxane 400g (the yield: 95%) of expression.
[synthesis example 2]
With blender, reflux condenser, thermometer four-hole boiling flask in, put into 1,3- divinyl -1,1,3,3- tetra- Tetramethyldisiloxane 54.7g (0.29mol), octamethylcy-clotetrasiloxane 87.1g (0.29mol), phenyltrimethoxysila,e 427.0g (2.15mol) and trifluoromethayl sulfonic acid 0.34g, under stiring, 30 minutes used times dropwise addition water 110.8g (6.15mol).After completion of dropwise addition, 85 DEG C are heated to, the methanol of production is distilled off.Put into toluene 105g and 30 mass percentages The potassium hydroxide aqueous solution 2.8g of ratio, makes water azeotropic dehydration.Later, it after 125 DEG C are kept for 6 hours, is cooled to room temperature, uses acetic acid 0.9g is neutralized.After being filtered to the salt of generation, heating decompression removal low boilers, system from clear solution obtained Standby colorless and transparent and number-average molecular weight be 1,800, with averaged unit formula:
(ViMe2SiO1/2)0.15(Me2SiO2/2)0.30(PhSiO3/2)0.55
Organopolysiloxane 400g (the yield: 95%) of expression.
[synthesis example 3]
With blender, reflux condenser, thermometer four-hole boiling flask in, put into 1,3- divinyl -1,1,3,3- tetra- Tetramethyldisiloxane 63.4g (0.34mol), 1,3,5,7- tetraphenyl -1,3,5,7- tetramethyl-ring tetrasiloxane 92.7g (0.17mol), phenyltrimethoxysila,e 404.9g (2.04mol) and trifluoromethayl sulfonic acid 0.35g, under stiring, the used time 30 minutes dropwise addition water 110.4g (6.13mol).After completion of dropwise addition, 85 DEG C are heated to, the methanol of production is distilled off.Put into toluene The potassium hydroxide aqueous solution 2.8g of 105g and 30 mass percents, make water azeotropic dehydration.Later, it is kept for 6 hours at 125 DEG C Afterwards, it is cooled to room temperature, is neutralized with acetic acid 0.9g.After being filtered to the salt of generation, add from clear solution obtained Heat decompression removal low boilers, prepare colorless and transparent and number-average molecular weight for 1,300, with averaged unit formula:
(ViMe2SiO1/2)0.20(PhMeSiO2/2)0.20(PhSiO3/2)0.60
Organopolysiloxane 400g (the yield: 95%) of expression.
[synthesis example 4]
With blender, reflux condenser, thermometer four-hole boiling flask in, put into 1,3- divinyl -1,1,3,3- tetra- Tetramethyldisiloxane 46.6g (0.25mol), 1,3,5,7- tetraphenyl -1,3,5,7- tetramethyl-ring tetrasiloxane 136.3g (0.25mol), phenyltrimethoxysila,e 363.8g (1.83mol) and trifluoromethayl sulfonic acid 0.35g, under stiring, the used time 30 minutes dropwise addition water 99.2g (5.50mol).After completion of dropwise addition, 85 DEG C are heated to, the methanol of production is distilled off.Put into toluene The potassium hydroxide aqueous solution 2.8g of 105g and 30 mass percents, make water azeotropic dehydration.Later, it is kept for 6 hours at 125 DEG C Afterwards, it is cooled to room temperature, is neutralized with acetic acid 0.9g.After being filtered to the salt of generation, add from clear solution obtained Heat decompression removal low boilers, prepare colorless and transparent and number-average molecular weight for Isosorbide-5-Nitrae 00, with averaged unit formula:
(ViMe2SiO1/2)0.15(PhMeSiO2/2)0.30(PhSiO3/2)0.55
Organopolysiloxane 400g (the yield: 95%) of expression.
[synthesis example 5]
It is put into the reaction vessel with formula:
HO(Me2SiO)12H
Dimethyl polysiloxane 40.0g (0.045mol), toluene 62.0g and the Trimethylamine 10.9g of expression (0.107mol) puts into vinyl diphenyl chlorosilane 22.0g (0.090mol) under stiring.After being stirred at room temperature 1 hour, 50 DEG C are heated to stir 3 hours.Later, water is put into, after being washed, evaporates low-boiling-point substance from organic layer heating decompression, preparation is viscous Degree be 36mPas, colorless and transparent and refractive index be 1.466, with formula:
ViPh2SiO(Me2SiO)12SiPh2Vi
The organopolysiloxane of expression.
[synthesis example 6]
With blender, reflux condenser, thermometer four-hole boiling flask in, put into 1,3- divinyl -1,1,3,3- tetra- Tetramethyldisiloxane 82.2g (0.44mol), water 143g, trifluoromethayl sulfonic acid 0.38g and toluene 500g, under stiring used time 1 hour dropwise addition phenyltrimethoxysila,e 524.7g (2.65mol).After dripping, heating is also flowed 1 hour.It is followed by cold But, and lower layer is separated, toluene solution layer is washed 3 times.3- glycidoxypropyl group is put into toluene solution layer after washing Methyl dimethoxysilane 314g (1.42mol), water 130g and potassium hydroxide 0.50g are heated to reflux 1 hour.Then, it evaporates Methanol removes superfluous water by azeotropic dehydration.After being heated to reflux 4 hours, cooling toluene solution is carried out with acetic acid 0.55g With then washing 3 times.After removing water, distillation removal toluene, is modulated into viscosity for 8,500mPas and with average under reduced pressure It is modular:
(ViMe2SiO1/2)0.18(PhSiO3/2)0.53(EpMeSiO2/2)0.29
The bonding agent of expression.
[Examples 1 to 5, comparative example 1~3]
Following compositions are mixed with forming (mass parts) shown in table 1, prepare hardenability silicon composition.It needs Bright, [SiH/Vi] expression in table 1 rubs relative to vinyl 1 contained in (A) ingredient ingredient corresponding with (B) ingredient You, the molal quantity contained in the corresponding ingredient of (C) ingredient with the hydrogen atom of silicon atom bonding.In addition, the content of (D) ingredient with Platinum in mass unit is indicated relative to the content (ppm) of hardenability silicon composition.
Use following compositions as (A) ingredient.
(A-1) ingredient: being prepared in synthesis example 1, with averaged unit formula:
(ViMe2SiO1/2)0.20(Me2SiO2/2)0.20(PhSiO3/2)0.60
Organopolysiloxane (containing ratio=12.5 of the vinyl relative to total organic group with silicon atom bonding of expression Mole %)
(A-2) ingredient: being prepared in synthesis example 2, with averaged unit formula:
(ViMe2SiO1/2)0.15(Me2SiO2/2)0.30(PhSiO3/2)0.55
Organopolysiloxane (containing ratio=9.4 of the vinyl relative to total organic group with silicon atom bonding of expression Mole %)
(A-3) ingredient: being prepared in synthesis example 3, with averaged unit formula:
(ViMe2SiO1/2)0.20(PhMeSiO2/2)0.20(PhSiO3/2)0.60
Organopolysiloxane (containing ratio=12.5 of the vinyl relative to total organic group with silicon atom bonding of expression Mole %)
(A-4) ingredient: being prepared in synthesis example 4, with averaged unit formula:
(ViMe2SiO1/2)0.15(PhMeSiO2/2)0.30(PhSiO3/2)0.55
Organopolysiloxane (containing ratio=9.4 of the vinyl relative to total organic group with silicon atom bonding of expression Mole %)
(A-5) ingredient: with averaged unit formula:
(ViMe2SiO1/2)0.25(PhSiO3/2)0.75
Organopolysiloxane (containing ratio=16.7 of the vinyl relative to total organic group with silicon atom bonding of expression Mole %)
Use following compositions as (B) ingredient.
(B-1) ingredient: the benzene that two end of strand of viscosity 2,000mPas is blocked by dimethylvinyl siloxy Ylmethyl polysiloxanes
(B-2): being prepared in synthesis example 5, with formula:
ViPh2SiO(Me2SiO)12SiPh2Vi
The organopolysiloxane of expression
Use following compositions as (C) ingredient.
(C-1) ingredient: viscosity 4mPas and with formula:
HMe2SiOPh2SiOSiMe2H
The organopolysiloxane of expression
(C-2) ingredient: viscosity 30mPas and with averaged unit formula:
(HMe2SiO1/2)0.6(PhSiO3/2)0.4
The organopolysiloxane of expression
Use following compositions as (D) ingredient.
(D-1) ingredient: the 1,3,5,7- tetramethyl of platinum -1,3- divinyl -1,1,3,3- tetramethyl disiloxane complex compound The solution (solution of the platinum containing 0.121 mass percent) of base -1,3,5,7- tetravinyl cyclotetrasiloxane
Use following compositions as (E) ingredient.
(E-1) ingredient: 1- ethynylcyclohexanol
Use following compositions as (F) ingredient.
(F-1) ingredient: the bonding agent prepared in synthesis example 6
By the result of table 1 it has been confirmed that compared with the hardenability silicon composition prepared in comparative example 1~3, Examples 1 to 5 In the hardenability silicon composition of middle preparation, the dispersibility hardening thing excellent, obtained of fluorophor it is cracking excellent.
Industrial utilizability
The favorable dispersibility of the fluorophor of hardenability silicon composition of the invention can be formed after hardening with cracking hard Compound, therefore can be used as the sealant of optical semiconductor in the optical semiconductor devices such as light emitting diode (LED), protection coating Agent etc..
Symbol description
1 optical semiconductor
2 lead frames
3 lead frames
4 bonding wires
5 frame parts
The hardening thing of 6 hardenability silicon compositions

Claims (8)

1. a kind of hardenability silicon composition, is at least made of following compositions:
(A) with averaged unit formula
(R1 3SiO1/2)x(R2 2SiO2/2)y(R3SiO3/2)z
The organopolysiloxane of expression, in formula, R1For identical or different carbon number be 1~12 alkyl, carbon number be 2~12 alkene The aralkyl that the aryl or carbon number that base, carbon number are 6~20 are 7~20, R2The alkane for being 1~12 for identical or different carbon number The alkenyl that base or carbon number are 2~12, R3For carbon number be 1~12 alkyl, carbon number be 6~20 aryl or carbon number be 7 ~20 aralkyl, wherein in a molecule, with the R1、R2And R3At least 0.5 molar percentage of the summation of the group of expression For the alkenyl, with the R3At least one of the group of expression is the aryl or the aralkyl, and x, y and z are respectively full The number of 0.01≤x≤0.5,0.01≤y≤0.4,0.1≤z≤0.9 and x+y+z=1 enough；
(B) relative to 100 mass parts (A) ingredient, with the straight-chain of at least two alkenyl in a molecule of 0.1~60 mass parts Organopolysiloxane；
(C) organopolysiloxane of the hydrogen atom in a molecule at least two and silicon atom bonding, wherein relative to (A) at Divide with 1 mole of alkenyl total amount contained in (B) ingredient, rubs contained by this ingredient with the hydrogen atom of silicon atom bonding for 0.1~10 Your amount；And
(D) hydrosilylation reactions catalyst, amount are to can promote the amount of this composition hardening.
2. hardenability silicon composition as described in claim 1, wherein (A) ingredient is organopolysiloxane, organic poly- silicon R in the averaged unit formula of oxygen alkane2The alkyl for being 1~12 for identical or different carbon number.
3. hardenability silicon composition as claimed in claim 1 or 2, wherein (B) ingredient is the silicon atom key of two end of strand Close the organopolysiloxane of the straight-chain of alkenyl.
4. hardenability silicon composition as claimed in claim 1 or 2, wherein further inhibit containing (E) hydrosilylation reactions Agent, (E) ingredient are 0.01~3 mass parts relative to (A) ingredient~(C) ingredient 100 mass parts of total.
5. hardenability silicon composition as claimed in claim 1 or 2, wherein further contain (F) bonding agent, it is described (F) Ingredient adds up to 100 mass parts to be 0.1~5 mass parts relative to (A) ingredient~(C) ingredient.
6. hardenability silicon composition as claimed in claim 1 or 2, wherein further contain (G) fluorophor, (G) ingredient It is 0.1~70 mass percent relative to (A) ingredient~(C) ingredient total amount.
7. a kind of hardening thing, which is characterized in that it hardens hardenability silicon composition described in any one of claims 1 to 6 It forms.
8. a kind of optical semiconductor device, which is characterized in that optical semiconductor is using described in any one of any one of claims 1 to 66 The hardened mass seals of hardenability silicon composition or covering.
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